CN109279745A - A kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal - Google Patents
A kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal Download PDFInfo
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- CN109279745A CN109279745A CN201811133764.2A CN201811133764A CN109279745A CN 109279745 A CN109279745 A CN 109279745A CN 201811133764 A CN201811133764 A CN 201811133764A CN 109279745 A CN109279745 A CN 109279745A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of methods that biodegradable chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal.First to sludge pretreatment, biological chelating agent stirring is added, electric device is then assembled and carries out electrokinetic process experiment.The present invention uses the H generated using electrolysis water in anode chamber+Under the action of electromigration and electro-osmosis, it is transferred to the chelating agent of generation acidification and mud room in sludge and generates chelation to collectively promote dissolution and the catholyte HNO of Heavy Metals in Sludge3Cathode pH is constantly regulate, three's collective effect obtains higher sludge removal efficiency.40.70-52.66% heavy metal is removed in sludge after processing, and content is lower than national standard.Electric device is kept the temperature using thermal insulation material, reduces thermal loss, using the electronic loss waste-heat sludge area of tradition, sludge temperature is maintained, to reduce process energy consumption.
Description
Technical field
The present invention relates to industrial sludge process fields, and in particular, to a kind of to be gone using novel chelating agents coupling electric driving method
Except the method for Desulphurization for Coal-fired Power Plant wastewater sludge heavy metal.
Background technique
Contain a large amount of SO in the flue gas that coal-burning power plant is discharged2And dust, serious pollution is caused to environment, to fire coal
It is to reduce SO that power plant, which carries out flue gas desulfurization,2The important method of discharge.Ended for the end of the year 2015, the coal motor of desulfurization equipment is installed in China
Group increases to 8.9 hundred million kilowatts by 5.8 hundred million kilowatts in 2010, and installation rate increases to 99% or more by 83%.Currently, lime
Stone-gypsum wet desulfurization is the technology that coal-burning power plant of China emphasis is promoted the use of.But Limestone-gypsum Wet Flue Gas Desulfurization Process technology
Be widely used desulfurization sludge yield caused increasingly to increase.With the coal motor of 2015 end of the year whole nation coal-burning power plants installation desulfurization equipment
Group total installation of generating capacity calculates, and unit operates normally for 24 hours, and the sludge quantity that year generates moisture content 70%~80% is about 9,000,000 tons.Such as
On the one hand this huge desulfurization sludge causes the waste of resource if disposed using landfill or by the way of burning, on the other hand
Additional contamination hazard can be caused to environment.Contain each Heavy Metallic Elements in power plant soot, when entering boiler combustion, in coal
Heavy metal element discharge in combustion, a part enter desulphurization system with flue gas after, be deposited in desulfurization sludge.This
Content of beary metal in a little sludge is seriously more than " urban sewage treatment plant sludge disposition-agricultural shale " (CJ/T309-
2009), " urban sewage treatment plant sludge disposition-afforestation shale " (CJ/T248-2007), " state of the People's Republic of China (PRC)
Family's standard soil environmental quality standards " standards such as (GB15618-1995).If these heavy metals can enter soil without processing
Earth or body of groundwater environment, and then influence the health of people.
Removing heavy metal method common at present has chemical leaching method, chemical restoration, thermochemical study method, phytoremediation
Method, bioleaching, united restoration method etc..However in place of the equal Shortcomings of these methods.Inorganic acid, organic acid of chemical method etc.
Acid consumption is big, somewhat expensive.Phytoremediation is influenced by geographical conditions, and a kind of plant usually only absorbs one two kinds of elements.Biology
Leaching method culture propagation speed is slow, the long treatment effect less stable of incubation time.Electric driving method is because easy to operate, quick, controllable
Property is strong, secondary pollution is few and by extensive concern.Traditional electric driving method is because adding mineral acid acidified, non-degradable chelating agent etc. causes
Acid consumption is big, and removal efficiency is low.Attempting research Biodegradable chelating agent coupling electrokinetic process technology is desulfurization wastewater dirt
Innoxious, resource utilization the new direction of mud.
Summary of the invention
Electronic removal is coupled in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of biodegradable chelating agent to take off
The method of sulphur wastewater sludge heavy metal.
The present invention is the technical problem solved in background technique, the technical solution adopted is that: a kind of biodegrade chelating agent
The method for coupling electronic removal desulfurization wastewater sludge heavy-metal, includes the following steps:
1) sludge pretreatment
Desulphurization for Coal-fired Power Plant wastewater sludge, natural air drying, filtering of being sieved after grinding；
The degradable biological chelating agent of 0.05mol/L is prepared by sludge heavy-metal total content；
A certain amount of chelating agent solution is added by liquid-solid ratio 1:3, mechanical stirring is uniformly mixed；
2) electric device assembles
It is placed in clip slot with cationic membrane, anode chamber and cathode chamber is separated with sludge region, will stood and chelating
The uniformly mixed sludge of agent pours into mud room, adds 250mL deionized water in anode chamber, adds 250mL in cathode chamber
0.1mol/LHNO3Solution stands for 24 hours, reaches osmotic balance；
It is inserted into graphite plate electrode in anode chamber and cathode chamber respectively, connects power supply；
Electrolyte is recycled in cathode chamber installation peristaltic pump；
Polyethylene and the external environment that one layer of 2cm thickness is wrapped up around electric device are heat-insulated；
3) electrolytic experiment
Under electric field action, anode chamber Zhong Shui is constantly electrolysed the H of generation+Under the action of electromigration and electro-osmosis, transfer
Acidification is generated into sludge to promote the dissolution of Heavy Metals in Sludge；
The chelating agent of mud room generates chelation, and the two jointly moves heavy metal under the action of electromigration and electro-osmosis
It moves on to cathode chamber and catholyte generates OH-Form indissoluble hydroxide precipitating；
Catholyte HNO3Cathode pH is constantly regulate, improves sludge removal efficiency to realize.
Biological chelating agent includes glutamic acid N, four sodium of N oxalic acid (GLDA), imino-diacetic amber in step 1) of the present invention
Amber four sodium of acid (IDS) and disodium ethylene diamine tetraacetate (Na2EDTA) solution.
Specific step is as follows for step 3) of the present invention:
(1) circuit and peristaltic pump connecting line are checked, opens power supply, it is 32V, voltage drop 1.6V/cm that setting voltage is constant,
Peristaltic pump is opened, flow velocity 0.37mL/min is set；
(2) under electric field action, anode chamber Zhong Shui is constantly electrolysed the H of generation+Under the action of electromigration and electro-osmosis, turn
It moves on in sludge and generates acidification to promote the dissolution of Heavy Metals in Sludge；
(3) chelating agent of mud room generates chelation, and the two jointly will a huge sum of money under the action of electromigration and electro-osmosis
Category moves to cathode chamber and catholyte generates OH-Indissoluble hydroxide is formed to precipitate, and catholyte HNO3Constantly regulate yin
Pole pH.
It keeps electrolyte solution property constant in step 2) of the present invention, updates within electrolyte solution every 24 hours primary protect
It holds the continuous operation of experiment and ensures the regularity of electrolyte addition.
Heavy Metals in Sludge of the present invention includes As, Cd, Cr, Cu, Hg, Ni, Pb, Zn.
The utility model has the advantages that
1, the H generated using electrolysis water in anode chamber+Under the action of electromigration and electro-osmosis, it is transferred in sludge and generates
The chelating agent of acidification and mud room generates chelation to collectively promote dissolution and the catholyte of Heavy Metals in Sludge
HNO3Cathode pH is constantly regulate, three's collective effect obtains relatively high sludge removal efficiency.
2, using biodegradable chelating agent, processing speed is fast, simple process, and removal efficiency is high, and the chelating agent of addition is raw
Biodegradable is good, environmentally friendly, does not influence the subsequent processing of sludge.
3, heat-insulated using polyethylene and external environment, thermal loss is reduced, system process energy consumption is reduced.
Detailed description of the invention
Fig. 1 is electrokinetic process experimental provision of the invention: a is planar dimension；B is device section.
Appended drawing reference: 1- constant voltage dc source；2- thermometer；3- peristaltic pump；4- peristaltic tube；5- reservoir；The anode chamber 6-；
7- graphite plate electrode；8- filter paper；9- mud room；10- cathode chamber
Specific embodiment
Come to make a step explanation to the present invention in the following with reference to the drawings and specific embodiments.Experimental provision is as shown in Figure 1.
Embodiment 1
Mud sample is derived from the desulfurization wastewater sludge after the wet desulphurization of Guangzhou coal-burning power plant, aqueous after mechanical dehydration
Rate 9.93%, solid content 90.07%, the content of beary metal such as table 1 in mud sample (butt).
Content of beary metal (mg/kg) in 1 mud sample of table (butt)
Sludge pretreatment: Desulphurization for Coal-fired Power Plant wastewater sludge is carried out first, and natural air drying crosses 80 mesh screens after grinding.
500g sludge is taken, the chelating agent GLDA solution of 0.05mol/L is prepared by sludge heavy-metal content, is added by liquid-solid ratio 1:3 certain
The chelating agent solution of amount, mechanical stirring are uniformly mixed.
Secondly, electric device assembles: be placed in clip slot with cationic membrane, by anode chamber and cathode chamber and sludge region every
It opens, the sludge stood is poured into mud room, add 250mL deionized water in anode chamber, add 250mL in cathode chamber
0.1mol/LHNO3Solution stands for 24 hours, reaches osmotic balance.Respectively in anode chamber and cathode chamber insertion graphite plate electricity
Pole is connected to power supply.Electrolyte is recycled in cathode chamber installation peristaltic pump.One layer of 2cm thickness is wrapped up around electric device
Polyethylene be thermally shielded.
Followed by electrolytic experiment: checking circuit and peristaltic pump connecting line, opens power supply, constant setting voltage is 32V, electricity
Pressure drop 1.6V/cm opens peristaltic pump, and flow velocity 0.37mL/min is arranged, and is electrolysed 120h.Under electric field action, anode chamber Zhong Shui is not
The H that power-off solution generates+With cathodic region HNO3Acidification is generated to promote the dissolution of Heavy Metals in Sludge, the chelating agent of mud room
Heavy metal transformation to cathode chamber and electrolysis are generated OH under the action of electromigration by chelation-It is heavy to form indissoluble hydroxide
It forms sediment.Per replacement once electrolytic matter solution for 24 hours.
After electronic experiment, the content of remaining As, Cd, Cr, Cu, Hg, Ni, Pb, Zn such as table 2 in sludge:
Sludge heavy-metal content (mg/kg) and removal rate (%) before and after 2 electrokinetic process of table
As can be seen that the removal efficiency of As, Cr, Hg, Ni, Pb, Zn are higher in sludge.The removal efficiency highest of Zn, Cd's
Removal efficiency is minimum, and comprehensive removal effect is good, meets national relevant emission standards.
Embodiment 2
Mud sample is derived from the desulfurization wastewater sludge after the wet desulphurization of Zhangjiakou coal-burning power plant and contains after mechanical dehydration
Water rate 10.23%, solid content 89.77%, the content of beary metal such as table 3 in mud sample (butt).
Content of beary metal (mg/kg) in 3 mud sample of table (butt)
Sludge pretreatment: Desulphurization for Coal-fired Power Plant wastewater sludge is carried out first, and natural air drying crosses 80 mesh screens after grinding.
500g sludge is taken, the chelating agent GLDA solution of 0.05mol/L is prepared by sludge heavy-metal content, is added by liquid-solid ratio 1:3 certain
The chelating agent solution of amount, mechanical stirring are uniformly mixed.
Secondly, electric device assembles: be placed in clip slot with cationic membrane, by anode chamber and cathode chamber and sludge region every
It opens, the sludge stood is poured into mud room, add 250mL deionized water in anode chamber, add 250mL in cathode chamber
0.1mol/LHNO3Solution stands for 24 hours, reaches osmotic balance.Respectively in anode chamber and cathode chamber insertion graphite plate electricity
Pole is connected to power supply.Electrolyte is recycled in cathode chamber installation peristaltic pump.The poly- of 2cm thickness is wrapped up around electric device
Vinyl foam is thermally shielded.
Then it carrying out electrolytic experiment: checking circuit and peristaltic pump connecting line, open power supply, constant setting voltage is 32V,
Voltage drop 1.6V/cm opens peristaltic pump, and flow velocity 0.37mL/min is arranged, and is electrolysed 120h.Under electrolysis, anode chamber Zhong Shui
The constantly H of electrolysis generation+With cathodic region HNO3Acidification is generated to promote the dissolution of Heavy Metals in Sludge, the chelating of mud room
Heavy metal transformation to cathode chamber and electrolysis are generated OH under the action of electromigration by agent chelation-Form indissoluble hydroxide
Precipitating.Per replacement once electrolytic matter solution for 24 hours.
After electronic experiment, the changes of contents of As, Cd, Cr, Cu, Hg, Ni, Pb, Zn in sludge are as shown in table 4.
Sludge heavy-metal content (mg/kg) and removal rate (%) before and after 4 electrokinetic process of table
As can be seen that the removal efficiency of As, Cr, Hg, Ni, Pb, Zn are higher in sludge.The removal efficiency highest of Zn, Cd's
Removal efficiency is minimum, and comprehensive removal effect is good, meets national relevant emission standards.
As can be seen that the present invention proposes that low-cost technologies scheme can effectively remove the heavy metal in desulfurization wastewater sludge,
While not changing sludge quality, nature soil environment is protected using biodegradable chelating agent, simultaneously because using
It is heat-insulated with external environment using polyethylene, thermal loss is reduced, system energy consumption utilization efficiency is reduced.To environmental protection and electricity
The utilization of resources of factory's desulfurization wastewater sludge has highly beneficial meaning.
Above-mentioned case is the present invention three kinds of chelating agents GLDA, IDS, Na2Optimal embodiment in EDTA, but it is of the invention
Embodiment is not limited by above-mentioned case, other are any to change, modify, replaces without departing from made under the principle of the present invention
In generation, simplifies combination, should be equivalent conversion regime, is included within the scope of the present invention.
Claims (5)
1. a kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal, which is characterized in that including
Following steps:
1) sludge pretreatment
Desulphurization for Coal-fired Power Plant wastewater sludge, natural air drying, filtering of being sieved after grinding；
The degradable biological chelating agent of 0.05mol/L is prepared by sludge heavy-metal total content；
A certain amount of chelating agent solution is added by liquid-solid ratio 1:3, mechanical stirring is uniformly mixed；
2) electric device assembles
It is placed in clip slot with cationic membrane, anode chamber and cathode chamber is separated with sludge region, mixed what is stood with chelating agent
It closes uniform sludge to pour into mud room, adds 250mL deionized water in anode chamber, add 250mL 0.1mol/ in cathode chamber
LHNO3Solution stands for 24 hours, reaches osmotic balance；
It is inserted into graphite plate electrode in anode chamber and cathode chamber respectively, connects power supply；
Electrolyte is recycled in cathode chamber installation peristaltic pump；
Polyethylene and the external environment that one layer of 2cm thickness is wrapped up around electric device are heat-insulated；
3) electrolytic experiment
Under electric field action, anode chamber Zhong Shui is constantly electrolysed the H of generation+Under the action of electromigration and electro-osmosis, it is transferred to sludge
It is middle to generate acidification to promote the dissolution of Heavy Metals in Sludge；
The chelating agent of mud room generates chelation, and the two jointly arrives heavy metal transformation under the action of electromigration and electro-osmosis
Cathode chamber and catholyte generate OH-Form indissoluble hydroxide precipitating；
Catholyte HNO3Cathode pH is constantly regulate, improves sludge removal efficiency to realize.
2. the side that a kind of biodegradable chelating agent according to claim 1 couples electronic removal desulfurization wastewater sludge heavy-metal
Method, which is characterized in that biological chelating agent includes glutamic acid N, four sodium of N oxalic acid (GLDA), imino-diacetic amber in the step 1)
Amber four sodium of acid (IDS) and disodium ethylene diamine tetraacetate (Na2EDTA) solution.
3. the side that a kind of biodegradable chelating agent according to claim 1 couples electronic removal desulfurization wastewater sludge heavy-metal
Method, which is characterized in that specific step is as follows for the step 3):
(1) circuit and peristaltic pump connecting line are checked, power supply is opened, constant setting voltage is 32V, voltage drop 1.6V/cm, is opened
Flow velocity 0.37mL/min is arranged in peristaltic pump；
(2) under electric field action, anode chamber Zhong Shui is constantly electrolysed the H of generation+Under the action of electromigration and electro-osmosis, it is transferred to
Acidification is generated in sludge to promote the dissolution of Heavy Metals in Sludge；
(3) chelating agent of mud room generates chelation, and the two jointly moves heavy metal under the action of electromigration and electro-osmosis
It moves on to cathode chamber and catholyte generates OH-Indissoluble hydroxide is formed to precipitate, and catholyte HNO3Constantly regulate cathode
pH。
To realize the purpose for improving sludge removal efficiency.In order to keep electrolyte solution property constant, electrolyte solution every 24
Hour updates the primary continuous operation for keeping experiment and ensures the regularity that electrolyte adds.
4. the method that biodegrade chelating agent according to claim 1 couples electronic removal desulfurization wastewater sludge heavy-metal,
It is characterized in that, heavy metal includes As, Cd, Cr, Cu, Hg, Ni, Pb, Zn in wastewater sludge.
5. the method that biodegrade chelating agent according to claim 1 couples electronic removal desulfurization wastewater sludge heavy-metal,
It is characterized in that, electrolyte solution every 24 hours in the step 2) update the primary continuous operation for keeping experiment.
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Cited By (8)
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| CN110342618A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学 | The device and method of processing pickle liquor and electroplating sludge is cooperateed with using electrodialytic technique |
| CN111170615A (en) * | 2020-01-09 | 2020-05-19 | 中国地质大学（武汉） | Method for removing heavy metals in sludge in enhanced manner by utilizing electroosmosis dehydration device |
| CN111302580A (en) * | 2020-04-01 | 2020-06-19 | 江西浩德实业有限公司 | Method for removing heavy metals in sludge |
| CN111875233A (en) * | 2020-07-30 | 2020-11-03 | 天津大学 | Quantitative analysis method for heavy metals in desulfurized sludge based on electric treatment |
| CN112058894A (en) * | 2020-08-11 | 2020-12-11 | 中国电建集团华东勘测设计研究院有限公司 | Method for carrying out enhanced electrokinetic remediation on heavy metal contaminated soil by GLDA (Global System for Mobile communications) |
| CN113526808A (en) * | 2021-07-19 | 2021-10-22 | 天津大学 | Preparation method of sludge-based biochar and sludge-based biochar |
| CN115477460A (en) * | 2022-11-14 | 2022-12-16 | 北京大臻科技有限公司 | Control method and system for separating and extracting sludge based on alkaline thermal hydrolysis machinery |
| CN115491206A (en) * | 2022-08-16 | 2022-12-20 | 中化地质矿山总局浙江地质勘查院 | Agent and method for repairing heavy metal contaminated soil |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342618A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学 | The device and method of processing pickle liquor and electroplating sludge is cooperateed with using electrodialytic technique |
| CN110342618B (en) * | 2019-06-17 | 2024-01-23 | 浙江大学 | Device and method for cooperatively treating pickling waste liquid and electroplating sludge by utilizing electrodialysis technology |
| CN111170615A (en) * | 2020-01-09 | 2020-05-19 | 中国地质大学（武汉） | Method for removing heavy metals in sludge in enhanced manner by utilizing electroosmosis dehydration device |
| CN111302580A (en) * | 2020-04-01 | 2020-06-19 | 江西浩德实业有限公司 | Method for removing heavy metals in sludge |
| CN111875233A (en) * | 2020-07-30 | 2020-11-03 | 天津大学 | Quantitative analysis method for heavy metals in desulfurized sludge based on electric treatment |
| CN111875233B (en) * | 2020-07-30 | 2022-11-04 | 天津大学 | Quantitative analysis method for heavy metals in desulfurized sludge based on electric treatment |
| CN112058894A (en) * | 2020-08-11 | 2020-12-11 | 中国电建集团华东勘测设计研究院有限公司 | Method for carrying out enhanced electrokinetic remediation on heavy metal contaminated soil by GLDA (Global System for Mobile communications) |
| CN113526808A (en) * | 2021-07-19 | 2021-10-22 | 天津大学 | Preparation method of sludge-based biochar and sludge-based biochar |
| CN115491206A (en) * | 2022-08-16 | 2022-12-20 | 中化地质矿山总局浙江地质勘查院 | Agent and method for repairing heavy metal contaminated soil |
| CN115477460A (en) * | 2022-11-14 | 2022-12-16 | 北京大臻科技有限公司 | Control method and system for separating and extracting sludge based on alkaline thermal hydrolysis machinery |
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